WO2014148737A1 - Procédé de préparation de biodiesel - Google Patents

Procédé de préparation de biodiesel Download PDF

Info

Publication number
WO2014148737A1
WO2014148737A1 PCT/KR2014/000886 KR2014000886W WO2014148737A1 WO 2014148737 A1 WO2014148737 A1 WO 2014148737A1 KR 2014000886 W KR2014000886 W KR 2014000886W WO 2014148737 A1 WO2014148737 A1 WO 2014148737A1
Authority
WO
WIPO (PCT)
Prior art keywords
raw oil
biodiesel
reaction
biodiesel raw
catalyst
Prior art date
Application number
PCT/KR2014/000886
Other languages
English (en)
Inventor
Tae Ho Ha
Eu Gene Jeon
Jung Hwan Ko
Jun U Yun
Seung Don Lee
Hyeok Park
Jin Sik Kwak
Kang Hoon Lee
Gyung Soo Kim
Original Assignee
M Energy Co., Ltd.
M Research Institute
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by M Energy Co., Ltd., M Research Institute filed Critical M Energy Co., Ltd.
Priority to CN201480000797.3A priority Critical patent/CN104321415A/zh
Priority to EP14747288.0A priority patent/EP2817395A4/fr
Priority to US14/377,085 priority patent/US20150322359A1/en
Publication of WO2014148737A1 publication Critical patent/WO2014148737A1/fr

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
    • C10L1/026—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only for compression ignition
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/32—Liquid carbonaceous fuels consisting of coal-oil suspensions or aqueous emulsions or oil emulsions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B3/00—Refining fats or fatty oils
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B3/00—Refining fats or fatty oils
    • C11B3/003—Refining fats or fatty oils by enzymes or microorganisms, living or dead
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B3/00—Refining fats or fatty oils
    • C11B3/008—Refining fats or fatty oils by filtration, e.g. including ultra filtration, dialysis
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B3/00—Refining fats or fatty oils
    • C11B3/02—Refining fats or fatty oils by chemical reaction
    • C11B3/04—Refining fats or fatty oils by chemical reaction with acids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B3/00—Refining fats or fatty oils
    • C11B3/02—Refining fats or fatty oils by chemical reaction
    • C11B3/06—Refining fats or fatty oils by chemical reaction with bases
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C1/00—Preparation of fatty acids from fats, fatty oils, or waxes; Refining the fatty acids
    • C11C1/08—Refining
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • C11C3/003—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fatty acids with alcohols
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2200/00—Components of fuel compositions
    • C10L2200/04—Organic compounds
    • C10L2200/0461—Fractions defined by their origin
    • C10L2200/0469—Renewables or materials of biological origin
    • C10L2200/0476—Biodiesel, i.e. defined lower alkyl esters of fatty acids first generation biodiesel
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2270/00—Specifically adapted fuels
    • C10L2270/02—Specifically adapted fuels for internal combustion engines
    • C10L2270/026—Specifically adapted fuels for internal combustion engines for diesel engines, e.g. automobiles, stationary, marine
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/08—Drying or removing water
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/26—Composting, fermenting or anaerobic digestion fuel components or materials from which fuels are prepared
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/54—Specific separation steps for separating fractions, components or impurities during preparation or upgrading of a fuel
    • C10L2290/542—Adsorption of impurities during preparation or upgrading of a fuel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

Definitions

  • the present invention relates to a method of preparing biodiesel.
  • Diesel oil is one of the fuels obtained from crude oil, and is advantageous in that it has high fuel efficiency, is low in price, and reduces the generation of carbon dioxide (CO 2 ).
  • Diesel oil is problematic in that it emits a large amount of air pollutants after combustion compared to other fuels obtained from crude oil.
  • Biodiesel is referred to as ester oil prepared by reacting various reproducible resources such as various plant oils including rapeseed oil, soybean oil, palm oil and the like, animal oils including beef tallow and the like, and waste cooking oils, etc. with alcohol in the presence of a catalyst. Since biodiesel has similar physical properties to diesel oil, it can be used for compression-ignition type diesel engines instead of diesel oil or in combination with diesel oil. That is, biodiesel may be defined as an alternative fuel to diesel oil, which is prepared by the chemical reaction of animal or plant fatty acid with methanol.
  • biodiesel is made by reacting aliphatic alcohol such as methanol with animal or plant oil, and, in this case, the yield and quality of biodiesel are determined depending on the properties of animal or plant oil used as a raw material for biodiesel.
  • the biodiesel produced using unpurified animal or plant oil as a raw material has many problems such as yield reduction during the synthesis process, quality deterioration and the like.
  • biodiesel raw oils containing lower fatty acids having an acid value of 5 mgKOH/g or more for example, lower waste cooking oil, palm acid oil obtained by the alkali-refining of palm oil, brown grease obtained from food waste, dark oil obtained from alkali oil ash (soap stock), white grease and yellow grease obtained by the primary refining of dark oil, trap grease obtained from ditches, drains or the like, and animal and plant oils and fats containing a large amount of non-purified impurities, include a large amount of particulate matter, gums, fatty acids, soaps, moisture and the like, and cause the deterioration of yield and quality of biodiesel in the process of preparing biodiesel by the fatty acid methyl esterification.
  • particulate matter included in waste cooking oil or animal and plant oils and fats containing a large amount of non-purified impurities causes problems of being an obstacle to a biodiesel preparing apparatus, decreasing the yield of biodiesel, contaminating a distillation process and deteriorating the quality of glycerin of a by-product.
  • FFA free fatty acid
  • an alkali catalyst in the synthesis of biodiesel to form soap and cause the loss of the alkali catalyst.
  • biodiesel and glycerin are emulsified due to the formed soap, and thus it is difficult to separate biodiesel and glycerin from each other, thereby decreasing the yield of biodiesel and deteriorating the quality of biodiesel.
  • biodiesel is hydrolyzed by the water to form FFA (free fatty acid), DAG (di-acyl glyceride) and MAG (mono-acyl glyceride).
  • the soap contained in a biodiesel raw oil or the soap component formed in the procedure of synthesis of biodiesel is emulsified with an oil fraction, so it is difficult to separate them from each other, with the result that the yield of biodiesel decreases, the quality of biodiesel deteriorates, the quality of glycerin as a by-product also deteriorates, and the post-treatment process of by-products becomes complicated.
  • Patent document 1 discloses a method of making a biodiesel raw oil by refining animal and plant oils and fats containing a large amount of impurities
  • Patent document 2 discloses a method of removing free fatty acid contained in waste cooking oil using a heterogeneous solid acid catalyst
  • Patent document 3 discloses a method of preparing biodiesel, wherein water included in alcohol recovered from a process of preparing biodiesel from oil and fat containing free fatty acid is removed by pervaporation, and is then resupplied into a reactor, so the action of water on esterification and trans-esterification reactions is reduced, thereby increasing the purity and yield of biodiesel.
  • biodiesel is prepared using a generally-known alkali catalyst, alkoxide catalyst, solid acid catalyst, metal catalyst or the like through a continuous or batch process.
  • alkali catalyst alkoxide catalyst
  • solid acid catalyst solid acid catalyst
  • metal catalyst metal catalyst
  • Patent document 1 Korean Patent Registration No. 10-0950280
  • Patent document 2 Koran Patent Application Publication No. 2004-0087625
  • Patent document 3 Koran Patent Application Publication No. 2009-0129619
  • the present inventors found that when a biodiesel raw oil is selectively pretreated according to the physical properties thereof to control the acid value of the biodiesel raw oil to a predetermined value or less, and then a combination of a biological catalyst process, a solid acid catalyst process and an alkali metal catalyst process is carried out, so the reactivity of a catalyst is efficiently increased, high-grade biodiesel, such as fuel for automobiles, can be economically prepared. Based on this finding, the present invention was completed.
  • an object of the present invention is to provide a method of economically and efficiently preparing biodiesel using a combination of a biological catalyst process, a solid acid catalyst process and an alkali metal catalyst process.
  • Another object of the present invention is to provide a method of economically and efficiently preparing biodiesel using a combination of an enzyme catalyst process, a solid acid catalyst process and an alkali metal catalyst process.
  • a first aspect of the present invention provides a method of preparing biodiesel, including the steps of: treating biodiesel raw oil containing lower fatty acid and having an acid value of 20 mgKOH/g or less with an adsorbent to remove foreign materials from the biodiesel raw oil; dewatering the purified biodiesel raw oil; passing the dewatered biodiesel raw oil through a solid acid catalyst reaction guard bed (Guard bed : PBR) provided with a cation exchange resin for removing metal cations, mixing methanol with the passed biodiesel raw oil, and then passing the mixture through a solid acid catalyst reaction main bed (Main Bed : PFR) provided with a solid acid catalyst for an esterification reaction to adjust the final acid value of the biodiesel raw oil to 5 mgKOH/g or less; and reacting the biodiesel raw oil having a final acid value of 5 mgKOH/g or less in the presence of an alkali catalyst.
  • a second aspect of the present invention provides a method of preparing biodiesel, including the steps of: treating biodiesel raw oil containing lower fatty acid and having an acid value of more than 20 mgKOH/g with an adsorbent to remove foreign materials from the biodiesel raw oil; passing the purified biodiesel raw oil through a continuous stirred tank reactor (CSTR) provided with an enzyme catalyst for an esterification reaction and a trans-esterification reaction in the presence of methanol, water and a buffer solution to adjust the acid value of the biodiesel raw oil to 20 mgKOH/g or less and adjust the content of FAME to 60% or less, and then separating glycerin; dewatering the biodiesel raw oil; passing the dewatered biodiesel raw oil through a solid acid catalyst reaction guard bed provided with a cation exchange resin for removing cations, mixing methanol with the biodiesel raw oil passed through the solid acid catalyst reaction guard bed, and then passing the mixture through a solid acid catalyst reaction main
  • the biodiesel raw oil having lower fatty acid may be at least one selected from the group consisting of waste lower cooking oil, palm acid oil, brown grease, white grease, yellow grease, dark oil, trap grease, and non-purified animal oils and fats.
  • the step of removing foreign materials may be performed by adding 0.1 ⁇ 5 wt% of an adsorbent at a reaction temperature of 30 ⁇ 150°C and a reaction time of 15 minutes ⁇ 3 hours.
  • the adsorbent may be at least one selected from the group consisting of diatomite, acidic white clay, active white clay, activated carbon and magnesium silicate.
  • the buffer solution not causing saponification may be at least one selected from the group consisting of a sodium bicarbonate solution, a sodium carbonate solution, a sodium phosphate solution, a 3-(N-morpholine)propanesulfonic acid solution, a (2-(N-morpholine)ethanesulfonic acid solution, a piperazine-N,N'-bis(2-ethanesulfonic acid) solution, and a (N-(2-hydroxyethyl)piperazine(2-ethanesulfonic acid) solution, and the buffer solution is added until the pH of the biodiesel raw oil is present in a range of 6 ⁇ 7.9.
  • water in the step of dewatering the biodiesel raw oil, water may be removed until the content of water is 0.1 wt% or less.
  • biodiesel raw oil for an enzyme catalyst reaction may be mixed with biodiesel raw oil containing no foreign materials and having an acid value of 20 mgKOH/g or less at a weight ratio of 1: 1 or more to adjust the content of FAME to 40% or less.
  • the enzyme catalyst reaction may be performed at a reaction temperature of 20 ⁇ 40°C using 20 ⁇ 60 parts by weight of a catalyst, 1 ⁇ 20 parts by weight of alcohol, 1 ⁇ 10 parts by weight of water, based on 100 parts by weight of the biodiesel raw oil, and a buffer solution capable of adjusting the pH of the biodiesel raw oil to 6 ⁇ 7.9.
  • the temperature condition may be 20 ⁇ 80°C, and pass rate may be 6 vol% (6 SV) or less in the solid acid catalyst reaction guard bed.
  • the temperature condition may be 70 ⁇ 120°C, and a flow rate may be 0.5 ⁇ 1.5 SV in the solid acid catalyst reaction main bed.
  • the alkali catalyst may be at least one selected from the group consisting of sodium methoxide (NaOCH 3 ), sodium hydroxide (NaOH), potassium methoxide (KOCH 3 ), and potassium hydroxide (KOH).
  • the step of reacting the biodiesel raw oil in the presence of an alkali catalyst may be performed at a reaction temperature of 50 ⁇ 80°C and a reaction time of 10 minutes ⁇ 2 hours.
  • Impurities are removed from a biodiesel raw oil containing a large amount of non-purified impurities by the pre-treatment of the biodiesel raw oil, thus solving the problems of obstructing the operation of a biodiesel preparing apparatus, decreasing the yield of biodiesel and making the separation of biodiesel and glycerin difficult after the synthesis of biodiesel.
  • methanol used in an enzyme catalyst reaction is not greatly influenced by the content of water, the methanol recovered after being used in the reaction can be reused without performing a dewatering process, so additional equipment is not needed, and a process cost can be reduced.
  • a general alkali catalyst process becomes complicated because it needs a deacidification process when a raw material containing a large amount of fatty acid.
  • the present invention is not influenced by the content of fatty acid, a process can be simplified, and the yield of biodiesel can be improved by converting FFA into biodiesel, not by removing FFA from a raw material.
  • glycerin which is a by-product obtained from a general alkali catalyst process, contains metal salts, its quality is lowered, and thus a complicated refining process for obtaining high-purity glycerin is necessarily required. However, since glycerin obtained in the present invention does not contain metal salts, a refining process can be simplified.
  • FIG. 1 is a schematic diagram showing a solid acid catalyst reactor including a guard bed and a main bed according to the present invention.
  • FIG. 2 is a flow diagram showing a process of preparing biodiesel according to the present invention.
  • biodiesel is prepared by reacting animal and plant oil and fat with aliphatic alcohol in the presence of an alkali catalyst to esterify the reactants.
  • an alkali catalyst a method of preparing biodiesel using an alkali catalyst is most frequently used.
  • the alkali catalyst sodium methoxide (NaOCH 3 ) is generally used, and sodium hydroxide (NaOH), potassium methoxide (KOCH 3 ), potassium hydroxide (KOH) or the like is used, too.
  • NaOH sodium hydroxide
  • KOH potassium hydroxide
  • the reason why relatively expensive sodium methoxide is generally used is that biodiesel can be obtained in a high yield even when a raw material contains water.
  • biodiesel preparation methods there are several biodiesel preparation methods. For example, there are, first, a method of preparing biodiesel by reacting animal and plant oil and fat with aliphatic alcohol at high temperature and high pressure in the presence of an acid catalyst such as sulfuric acid; second, a method of preparing biodiesel by hydrolyzing animal and plant oil and fat into fatty acid and then reacting the fatty acid with aliphatic alcohol in the presence of an acid catalyst; third, a method of preparing biodiesel by reacting animal and plant oil and fat with aliphatic alcohol using an insoluble catalyst such as barium oxide; and, fourth, a method of preparing biodiesel by reacting animal and plant oil and fat with aliphatic alcohol using an enzyme catalyst such as lipase, and the like.
  • an acid catalyst such as sulfuric acid
  • second a method of preparing biodiesel by hydrolyzing animal and plant oil and fat into fatty acid and then reacting the fatty acid with aliphatic alcohol in the presence of an
  • the present invention provides a method of economically and efficiently preparing biodiesel from biodiesel raw oil containing lower fatty acid and having an acid value of 5mgKOH/g or more and a maximum acid value of 200 mgKOH/g.
  • an adsorbent is added to biodiesel raw oil containing lower fatty acid and having an acid value of 5mgKOH/g or more and a maximum acid value of 200 mgKOH/g to remove a large amount of foreign materials, such as particulate matter, gums, soaps, moisture and the like, from the biodiesel raw oil.
  • the biodiesel raw oil (hereinafter, referred to as "raw oil") having lower fatty acid may be at least one selected form the group consisting of lower waste cooking oil, palm acid oil, brown grease, white grease, yellow grease, dark oil, trap grease, and non-purified animal oils and fats.
  • the raw oil is not limited thereto, and all raw oils may be used as long as they can be used as the raw material of biodiesel.
  • Lower fatty acids such as brown grease and the like, contain various sizes of foreign materials according to the generation source thereof, and produce bad odors. Therefore, various kinds of filter aids may be used, but, in the present invention, an adsorbent is preferably used because it has excellent adsorptivity, deodorization ability and humidity control performance to exhibit the effects of adsorbing foreign materials, removing bad smells and reducing humidity in the lower fatty acid.
  • the adsorbent exhibiting such effects may include diatomite, white clay (acidic white clay, active white clay, etc.), activated carbon and/or magnesium (magnesium silicate). Diatomite is preferred as adsorbent.
  • the amount of the adsorbent may be 0.1 ⁇ 5 wt%. When the amount thereof is less than 0.1 wt%, the addition effect thereof is insufficient, and, when the amount thereof is more than 5 wt%, the adsorbent is apt to absorb the raw oil, which is not preferred.
  • the adsorption reaction is performed at a temperature of 30 ⁇ 150°C, preferably, 50 ⁇ 80°C.
  • the lower raw oil such as brown grease, lower waste cooking oil, palm acid oil, yellow grease, dark oil or the like, may include a large amount of saturated fatty acid according to the source thereof.
  • the fluidity of the raw oil is lowered at room temperature. Therefore, in order to guarantee the fluidity thereof, the raw oil is heated (the heating temperature of the raw oil is changed depending on the content of saturated fatty acid in the raw oil), thus sufficiently and effectively reacting the raw oil with the adsorbent.
  • the adsorption reaction in the pre-treatment process may be performed at a reaction temperature of 30 ⁇ 150°C and a reaction time of 15 minutes ⁇ 3 hours.
  • the ability of the adsorbent to adsorb foreign materials is best when the adsorption reaction is performed at a reaction temperature of 50 ⁇ 80°C and a reaction time of 30 minutes ⁇ 1.5 hours.
  • the raw oil mixed with the adsorbent is filtered by a filter press, a leaf filter or a centrifugal separator. After the filtering, it is preferred that the filtered raw oil contain particles of 1 ⁇ m or less in an amount of 1 wt% or less.
  • this filtered raw oil is referred to as "pretreated raw oil” or "pretreatment-finished raw oil”.
  • raw oil 10 having an acid value of 20 mgKOH/g or less is pretreated as above, and then the pretreated raw oil is dewatered to remove water until the content of water is 0.1 wt% or less.
  • the dewatered raw oil is passed through a solid acid catalyst reaction guard bed 20 (PBR: packed bed reactor) provided with a cation exchange resin for removing cations, mixed with methanol in a mix tank 30, and then supplied to a solid acid catalyst reaction main bed 50 (PFR: plug flow reactor) provided with a solid acid catalyst for an esterification reaction by a pump 40 to perform a solid acid catalyst reaction.
  • PBR packed bed reactor
  • PFR plug flow reactor
  • This reaction product is condensed by a condenser 70, and then transferred to a subsequent process.
  • the reaction is finished.
  • the acid value of the raw oil is more than 5 mgKOH/g, methanol is recovered, and the raw oil is further passed through the solid acid catalyst reaction main bed to adjust the final acid value of the biodiesel raw oil to 5 mgKOH/g or less, preferably, 2 mgKOH/g or less, which is suitable for maximizing the efficiency of the following alkali catalyst process.
  • the reason for removing water in the raw oil is that water is produced with the occurrence of the solid acid catalyst reaction using a solid acid catalyst for an esterification reaction, and the produced water causes a reverse reaction, and thus the acid value of the raw oil exceeds the target acid value 5 mgKOH/g.
  • the reason for removing metal cations from the raw oil is that the metal cations cause a substitution reaction together with hydrogen ion (H + ) to deteriorate the activity of the solid acid catalyst, thus reducing the life time of the solid acid catalyst.
  • the reason for using raw oil having an acid value of 20 mgKOH/g or less is that it is difficult to attain the target acid value 5 mgKOH/g of the raw oil (product).
  • the raw oil having an acid value of more than 20 mgKOH/g is pretreated, and is then sequentially supplied to first and second continuous stirred tank reactors (CSTRs), each being provided with an enzyme catalyst for an esterification reaction and a trans-esterification reaction, to perform an enzyme catalyst reaction until the acid value of the enzyme catalyst reaction product (raw oil) is 20mgKOH/g or less.
  • CSTRs continuous stirred tank reactors
  • glycerin is produced, and this glycerin is separated by gravity separation or centrifugal separation.
  • Raw oil for an enzyme catalyst reaction is mixed with raw oil containing no foreign materials and having an acid value of 20 mgKOH/g or less at a weight ratio of 1: 1 or l: 2 or more (for example, 1:2, 1:3, etc.). Then, the mixed raw oil is dewatered to remove water and methanol, and is then sequentially supplied to a solid acid catalyst reaction guard bed (PBR) provided with a cation exchange resin for removing cations and a solid acid catalyst reaction main bed (PBR) provided with a solid acid catalyst for an esterification reaction to perform a solid acid catalyst reaction.
  • PBR solid acid catalyst reaction guard bed
  • PBR solid acid catalyst reaction main bed
  • the reason for mixing the raw oil for an enzyme catalyst reaction with the raw oil containing no foreign materials and having an acid value of 20 mgKOH/g or less at a weight ratio of 1: 1 or l: 2 or more is that, when the content of fatty acid methyl ether (FAME) in the raw oil, the solid acid catalyst for an esterification reaction causes a reverse reaction due to the water produced during the solid acid catalyst reaction, and thus the acid value of the raw oil (product) exceeds the target acid value 5 mgKOH/g.
  • FAME fatty acid methyl ether
  • the pretreated raw oil is mixed with methanol, water and a buffer solution, and then the mixture is reacted in a continuous stirred tank reactor (CSTR) provided with an enzyme catalyst for an esterification reaction and a trans-esterification reaction.
  • CSTR continuous stirred tank reactor
  • the buffer solution which is a solution changing the pH of reactants to the neutral position by neutralizing the reactants while not participating in a reaction, must not cause saponification.
  • all buffer solutions having a pKa of 9 or more may be used without limitation as long as they do not create by-products such as soap and the like while adjusting pH.
  • Examples of the buffer solution not causing saponification may include: a sodium bicarbonate solution; a sodium carbonate solution; a sodium phosphate solution such as Na 2 HPO 4 ⁇ 2H 2 O or NaH 2 PO 4 ⁇ 2H 2 O; a 3-(N-morpholine)propanesulfonic acid solution; and a ethanesulfonic acid solution such as a (2-(N-morpholine)ethanesulfonic acid solution, a piperazine-N,N'-bis(2-ethanesulfonic acid) solution or a (N-(2-hydroxyethyl)piperazine(2-ethanesulfonic acid) solution.
  • a sodium bicarbonate solution such as Na 2 HPO 4 ⁇ 2H 2 O or NaH 2 PO 4 ⁇ 2H 2 O
  • a 3-(N-morpholine)propanesulfonic acid solution such as a (2-(N-morpholine)ethanesulfonic acid solution, a piperazine-
  • the buffer solution is added until the pH of the raw oil is present in a range of 6 ⁇ 7.9, and the raw oil having the above range of pH can maximize the activity of an enzyme catalyst in the process of preparing biodiesel.
  • the buffer solution can adjust the pH of the raw oil, and must not cause saponification.
  • saponification is caused, so a subsequent process of removing soap is required, and the yield of biodiesel is remarkably lowered.
  • the enzyme catalyst used in the present invention 40 or more kinds of lipases and phospholipases can be commercially used, but, it is preferred that a circular plastic carrier having an outer diameter of 2 ⁇ 3 mm be supported with this enzyme catalyst.
  • biodiesel raw oils applicable to the present invention for example, purified raw oils such as soybean oil, rapeseed oil, palm oil and the like can be used without pretreatment.
  • biodiesel can be prepared using one or two or more mixture selected from the group consisting of palm acid oil, waste cooking oil, brown grease, dark oil, white grease, yellow grease, tap grease and non-purified animal and plant oils and fats.
  • biodiesel may also be prepared using a raw oil containing fatty acid generated from crude glycerin produced in the biodiesel preparation process.
  • the biodiesel raw oil may be used without limitation as long as it has a pH of 6 ⁇ 8 and contains particles having a diameter of 1 ⁇ m or less in an amount of 1 wt% or less.
  • the raw oil is sequentially supplied to first and second continuous stirred tank reactors (CSTRs) provided with an enzyme catalyst for an esterification reaction and a trans-esterification reaction in the presence of alcohol, water and/or a buffer solution according to the measured acid value of the raw oil.
  • CSTRs continuous stirred tank reactors
  • the enzyme catalyst for an esterification reaction and a trans-esterification reaction is a catalyst synthesizing fatty acid methyl ester (FAME) by an esterification reaction of FFA or a trans-esterification reaction of mono-glyceride, di-glyceride or tri-glyceride.
  • FAME fatty acid methyl ester
  • the enzyme catalyst reaction is performed at 20 ⁇ 40°C.
  • the enzyme catalyst is used in an amount of 20 ⁇ 60 parts by weight, alcohol is used in an amount of 1 ⁇ 20 parts by weight, and water is used in an amount of 1 ⁇ 10 parts by weight, based on 100 parts by weight of the biodiesel raw oil.
  • the buffer solution is added such that the pH of the raw oil is 6 ⁇ 7.9.
  • the content of water in the raw oil (feed) may be controlled to be 0.1 wt% or less.
  • the pretreated dewatered raw oil and the dewatered product of the enzyme product may pass through solid acid catalyst reaction guard bed (cation exchange resin) in a down-flow manner to remove metal cations. In this case, this process is performed at 20 ⁇ 80°C, and they are passed through the guard bed at a flow rate of 6 vol% (6SV) or less.
  • the pretreated (foreign matter-removed, dewatered and cation-removed) raw oil is mixed with methanol (10 ⁇ 50 wt%, based on raw oil), or methanol of enzyme catalyst reaction product, and then the mixture is sequentially passed through first and second packed bed reactors (PBRs) provided with a solid acid catalyst for an esterification reaction to conduct a solid catalyst reaction in an up-flow manner (reaction temperature: 70 ⁇ 120°C, reaction flow rate: 0.5 ⁇ 1.5 SV, reactor in-out p: 2.0 kgf/cm 2 or less).
  • PBRs packed bed reactors
  • an alkali catalyst method is generally used.
  • an alkali catalyst sodium methoxide (NaOCH3), sodium hydroxide (NaOH), potassium methoxide (KOCH3), and/or potassium hydroxide (KOH) may be used.
  • a potassium hydroxide catalyst when the acid value of the product in the previous process is 2 to 5 mgKOH/g and the water content thereof is less than 0.5 wt%, a potassium hydroxide catalyst is used; when the acid value thereof is 2 mgKOH/g or less and the water content thereof is less than 0.5 wt%, a sodium hydroxide catalyst is used; when the acid value thereof is 2 to 5 mgKOH/g and the water content thereof is 0.5 to 1 wt%, a potassium methoxide catalyst is used; and when the acid value thereof is 2 mgKOH/g or less and the water content thereof is 0.5 to 1 wt%, a sodium methoxide catalyst is used.
  • the acid value of raw oil is 5.0 mgKOH/g or more
  • the yield of biodiesel is rapidly reduced after an alkali metal catalyst reaction, thus decreasing economical efficiency, and the acid value thereof does not meet the quality standard (5.0 mgKOH/g or less) of an automobile fuel, and thus it is preferred that raw oil having an acid value of 5.0 mgKOH/g or less be used.
  • Biodiesel and glycerin are produced by reacting the product obtained from the solid acid catalyst process at a reaction temperature of 50 ⁇ 80°C for 10 minutes ⁇ 2 hours using the above solid acid catalyst according to the acid value and water content thereof.
  • the glycerin is separated by gravimetric separation or centrifugal separation.
  • the alkali catalyst process may be performed by mixing a new high-grade raw oil having an acid value of 5 mgKOH/g or less with the product obtained from the solid acid catalyst process.
  • the alkali catalyst reaction may be performed by adding insufficient methanol.
  • the above conductions are preferred in terms of economical profit and reaction efficiency.
  • biodiesel raw oil 20 g of diatomite was added to 1000 g of raw oil (FFA: about 10%, tri-glyceride: about 90%) having an acid value of about 19.8 mgKOH/g, and then reacted at about 70°C for about 1 hour to obtain biodiesel raw oil.
  • the obtained biodiesel raw oil includes about 0.6 wt% of particles having a diameter of 1 ⁇ m or less.
  • a solid acid catalyst of guard bed for removing cations may be provided with a cation exchange resin of K2629TM (manufactured by LANXESS Corporation in Germany).
  • a solid acid catalyst of main bed for an esterification reaction may be provided with GF-101TM (manufactured by LANXESS Corporation in Germany) of polymer resin supported SO 3 H + .
  • the raw oil having passed through the solid acid catalyst guard bed was mixed with methanol, and the mixture was reacted in the solid acid catalyst main bed, thus obtaining raw oil having an acid value of 1.94 mgKOH/g.
  • biodiesel raw oil 20 g of diatomite was added to 1000 g of raw oil having an acid value of about 49.4 mgKOH/g (FFA: about 24.7%, tri-glyceride: about 75.3%), and then reacted at about 70°C for about 1 hour to obtain biodiesel raw oil.
  • the obtained biodiesel raw oil includes about 0.5 wt% of particles having a diameter of 1 ⁇ m or less.
  • the biodiesel raw oil was reacted according to the reaction order shown in the application 2 of FIG. 2 under the reaction condition given in Table 4 below.
  • a CSTR was provided with an enzyme catalyst (TRANSZYMETM manufactured by TRASBIODIESEL Corporation in Israel) in which lipase is supported with plastic.
  • a solid acid catalyst guard bed for removing cations was provided with a cation exchange resin (K2629TM manufactured by LANXESS Corporation in Germany).
  • a solid acid catalyst main bed for an esterification reaction was provided with a polymer resin (GF-101TM manufactured by LANXESS Corporation in Germany) supported with SO 3 H + .
  • glycerin which is a by-product of an enzyme catalyst reaction in CSTR, water and the like were removed from the pretreated raw oil.
  • This raw oil was mixed with the pretreated raw oil having an acid value of 20 mgKOH/g or less at a ratio of 1: 1 (wt%), dewatered, and then supplied to a solid acid catalyst guard bed.
  • the raw oil having passed through the solid acid catalyst guard bed was mixed with methanol, and the mixture was reacted in the solid acid catalyst main bed, thus obtaining raw oil having an acid value of 1.91 mgKOH/g.
  • biodiesel raw oil 20 g of diatomite was added to 1000 g of raw oil (FFA: about 49.75%, tri-glyceride: about 50.25%) having an acid value of about 99.5 mgKOH/g, and then reacted at about 70°C for about 1 hour to obtain biodiesel raw oil.
  • the obtained biodiesel raw oil includes about 0.4 wt% of particles having a diameter of 1 ⁇ m or less.
  • the biodiesel raw oil was reacted according to the reaction order shown in the application 2 of FIG. 2 under the reaction condition given in Table 5 below.
  • a CSTR was provided with an enzyme catalyst (TRANSZYMETM manufactured by TRASBIODIESEL Corporation in Israel) in which plastic is supported with lipase,
  • a solid acid catalyst guard bed for removing cations was provided with a cation exchange resin (K2629TM manufactured by LANXESS Corporation in Germany), and
  • a solid acid catalyst main bed for an esterification reaction was provided with a polymer resin (GF-101TM manufactured by LANXESS Corporation in Germany) supported with SO 3 H + .
  • biodiesel raw oil 20 g of diatomite was added to 1000 g of raw oil (FFA: about 74.3%, tri-glyceride: about 25.7%) having an acid value of about 148.6 mgKOH/g, and then reacted at about 70°C for about 1 hour to obtain biodiesel raw oil.
  • the obtained biodiesel raw oil includes about 0.6 wt% of particles having a diameter of 1 ⁇ m or less.
  • the biodiesel raw oil was reacted according to the reaction order shown in the application 2 of FIG. 2 under the reaction condition given in Table 6 below.
  • a CSTR was provided with an enzyme catalyst (TRANSZYMETM manufactured by TRASBIODIESEL Corporation in Israel) in which plastic is supported with lipase, a solid acid catalyst guard bed for removing cations was provided with a cation exchange resin (K2629TM manufactured by LANXESS Corporation in Germany), and a solid acid catalyst main bed for an esterification reaction was provided with a polymer resin (GF-101TM manufactured by LANXESS Corporation in Germany) supported with SO 3 H + .
  • TRANSZYMETM manufactured by TRASBIODIESEL Corporation in Israel
  • the reaction product in the solid acid catalyst main bed 1 was dewatered to remove water and methanol therefrom, further mixed with methanol in the sold acid catalyst main bed 2 and then reacted, thus obtaining raw oil having an acid value of 2.04 mgKOH/g.
  • the sodium methoxide catalyst used in an alkali catalyst reaction was NM25TM (manufactured by EVONIK Corporation in Germany). 100 parts by weight of the raw oil was uniformly mixed with 2.0 parts by weight of sodium methoxide (NaOCH 3 ) and then reacted at about 70°C for about 0.5 hour to obtain biodiesel and glycerin.
  • the yield of biodiesel to raw oil was about 98 parts by weight, and the yield of glycerin to raw oil was about 6 parts by weight.
  • the obtained biodiesel has an acid value of 0.16 mgKOH/g and contains 97.8% or more of FAME.
  • the potassium methoxide catalyst used in an alkali catalyst reaction was KM32TM (manufactured by EVONIK Corporation in Germany). 100 parts by weight of the raw oil was uniformly mixed with 1.5 parts by weight of potassium methoxide (KOCH 3 ) and then reacted at about 70°C for 30 minutes to obtain biodiesel and glycerin.
  • the yield of biodiesel to raw oil was about 98 parts by weight, and the yield of glycerin to raw oil was about 6 parts by weight.
  • the obtained biodiesel has an acid value of 0.17 mgKOH/g and contains 97.4% or more of FAME.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Microbiology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Biochemistry (AREA)
  • Fats And Perfumes (AREA)
  • Liquid Carbonaceous Fuels (AREA)

Abstract

La présente invention concerne un procédé de préparation de biodiesel, comprenant les étapes consistant à : éliminer des substances étrangères d'une huile brute de biodiesel contenant des acides gras inférieurs et ayant un indice d'acide inférieur ou égal à 20 mgKOH/g avec un adsorbant ; sécher l'huile brute de biodiesel dont les substances étrangères ont été éliminées ; passer l'huile brute de biodiesel séchée à travers un lit de garde de réaction à catalyseur solide acide pourvu d'une résine échangeuse de cations pour éliminer les cations métalliques à 20 ~ 80 ℃ à un débit inférieur ou égal à 6 % en volume (6 SV), mélanger du méthanol à l'huile brute de biodiesel passée, et puis passer le mélange à travers un lit principal de réaction à catalyseur solide acide pourvu d'un catalyseur solide acide pour une réaction d'estérification à 70 ~ 120 ℃ à un débit de 0,5 ~ 1,5 SV pour ajuster un indice d'acide final de l'huile brute de biodiesel à une valeur inférieure ou égale à 5 mgKOH/g ; et faire réagir l'huile brute de biodiesel ayant un indice d'acide final inférieur ou égal à 5 mgKOH/g en présence d'un catalyseur alcalin.
PCT/KR2014/000886 2013-03-20 2014-01-29 Procédé de préparation de biodiesel WO2014148737A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN201480000797.3A CN104321415A (zh) 2013-03-20 2014-01-29 制备生物柴油的方法
EP14747288.0A EP2817395A4 (fr) 2013-03-20 2014-01-29 Procédé de préparation de biodiesel
US14/377,085 US20150322359A1 (en) 2013-03-20 2014-01-29 Method for preparing biodiesel

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR1020130029572A KR101355141B1 (ko) 2013-03-20 2013-03-20 바이오디젤의 제조방법
KR10-2013-0029572 2013-03-20

Publications (1)

Publication Number Publication Date
WO2014148737A1 true WO2014148737A1 (fr) 2014-09-25

Family

ID=50146358

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2014/000886 WO2014148737A1 (fr) 2013-03-20 2014-01-29 Procédé de préparation de biodiesel

Country Status (6)

Country Link
US (1) US20150322359A1 (fr)
EP (1) EP2817395A4 (fr)
KR (1) KR101355141B1 (fr)
CN (1) CN104321415A (fr)
TW (1) TWI486433B (fr)
WO (1) WO2014148737A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101863359B1 (ko) * 2015-07-01 2018-06-01 한국에너지기술연구원 바이오오일의 연속 촉매 반응 장치
CN105567434A (zh) * 2015-12-31 2016-05-11 山东泰德新能源有限公司 一种高清洁生物柴油的生产装置及方法
CN112625805A (zh) * 2020-09-23 2021-04-09 武汉科技大学 一种固体酸催化剂催化合成生物柴油的方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007176973A (ja) * 2005-12-27 2007-07-12 Lion Corp 軽油代替燃料用の脂肪酸低級アルキルエステルの製造方法
JP2009114272A (ja) * 2007-11-05 2009-05-28 Asahi Kasei Corp 固体酸触媒による脂肪酸モノエステル化物の製造方法
KR100961215B1 (ko) * 2008-06-13 2010-06-03 한국에너지기술연구원 유리지방산을 포함하는 원료유로부터 바이오디젤의제조방법
KR20130004286A (ko) * 2010-03-01 2013-01-09 트랜스 바이오디젤 엘티디. 지방산 알킬 에스테르의 효소적 합성을 위한 방법

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2611347A1 (fr) * 2005-06-09 2006-12-14 Biosphere Environmental Energy Llc Systemes et procedes d'esterification et de transesterification de graisses et d'huiles
WO2009060746A1 (fr) * 2007-11-05 2009-05-14 Tokyo Institute Of Technology Procédé de production d'un produit monoestérifié d'acide gras utilisant un catalyseur acide solide
US8097049B2 (en) * 2008-02-07 2012-01-17 The Dallas Group Of America, Inc. Biodiesel purification by a continuous regenerable adsorbent process
CN102021207B (zh) * 2010-11-04 2013-08-14 清华大学 一种在线脱水的脂肪酶催化可再生油脂制备生物柴油工艺
CN102311883B (zh) * 2011-08-10 2013-04-24 北京清研利华石油化学技术有限公司 一种制备高纯度生物柴油的方法
US8540881B1 (en) * 2012-11-27 2013-09-24 Menlo Energy Management, LLC Pretreatment, esterification, and transesterification of biodiesel feedstock

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007176973A (ja) * 2005-12-27 2007-07-12 Lion Corp 軽油代替燃料用の脂肪酸低級アルキルエステルの製造方法
JP2009114272A (ja) * 2007-11-05 2009-05-28 Asahi Kasei Corp 固体酸触媒による脂肪酸モノエステル化物の製造方法
KR100961215B1 (ko) * 2008-06-13 2010-06-03 한국에너지기술연구원 유리지방산을 포함하는 원료유로부터 바이오디젤의제조방법
KR20130004286A (ko) * 2010-03-01 2013-01-09 트랜스 바이오디젤 엘티디. 지방산 알킬 에스테르의 효소적 합성을 위한 방법

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP2817395A4 *

Also Published As

Publication number Publication date
KR101355141B1 (ko) 2014-01-29
EP2817395A4 (fr) 2015-10-21
US20150322359A1 (en) 2015-11-12
CN104321415A (zh) 2015-01-28
TWI486433B (zh) 2015-06-01
EP2817395A1 (fr) 2014-12-31
TW201439301A (zh) 2014-10-16

Similar Documents

Publication Publication Date Title
US8088183B2 (en) Production of biodiesel and glycerin from high free fatty acid feedstocks
CN101735882B (zh) 一种废内燃机油再生基础油的方法
WO2014148737A1 (fr) Procédé de préparation de biodiesel
US20060225341A1 (en) Production of biodiesel
US7534923B2 (en) Method for purification of glycerol from biodiesel production
WO2015012538A1 (fr) Procédé de préparation d'ester alkylique d'acide gras à partir de graisse
CA2552371A1 (fr) Procede ameliore permettant de preparer des alkylesters d'acides gras utilisables en tant que biodiesel
CN101067091A (zh) 一种由高酸值原料固相催化连续制备生物柴油的工艺
JP3028282B2 (ja) 廃食用油を原資源として精製する重油バーナー用燃料および廃食用油を原資源としての再利用方法
EP2159212B1 (fr) Procédé pour la purification de glycérol pour la production de biodiesel
JP4854889B2 (ja) 廃食油からのディーゼル燃料油の製造方法
KR101285828B1 (ko) 바이오디젤 원료유의 전처리 방법
KR100798605B1 (ko) 유색 원료유지로부터 바이오디젤의 제조공정 중 불균일계흡착제를 이용한 바이오디젤의 정제방법
JPWO2008053837A1 (ja) 燃料
KR101285830B1 (ko) 바이오디젤의 제조방법
US20170314047A1 (en) Method for the production of alkyl esters
WO2010147338A2 (fr) Biodiesel obtenu à partir de sous-produits de biodiesel et son procédé de fabrication
JP2014122317A (ja) バイオディーゼル燃料製造システム及びバイオディーゼル燃料製造方法
JP7252588B2 (ja) バイオディーゼル燃料の製造方法
WO2023120912A1 (fr) Procédé de production de biodiesel à l'aide de lipides d'origine animale et d'élimination du soufre
JP5553258B2 (ja) 脂肪酸アルキルエステルの製造方法
WO2013165217A1 (fr) Procédé pour la production de biodiesel utilisant des microorganismes sans processus de séchage
TWI297357B (en) System for continuously producing biodiesel
KR20230086341A (ko) 염기 촉매를 이용한 지방산 에스테르로부터 지방산 아마이드의 제조 방법
JP2010265335A (ja) 脂肪酸アルキルエステル燃料油の製造方法と製造装置

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 14377085

Country of ref document: US

REEP Request for entry into the european phase

Ref document number: 2014747288

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 2014747288

Country of ref document: EP

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14747288

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE